Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
21 88779
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Process for the preparation of 2,5-dimeth~1-2,5-
dih~droperoxyhexane
D~SCRIPTION
The invention concerns a process for the prepsration
of 2,5-dimethyl-2,5-dihy~roperoxghexane bg reaction of
2,5-dimeth~1-1,5-hexsdiene with hgdrogen peroxide iD an
acidic medium.
2,5-Dimethyl-2,5-dih~droperox~hexane (DHHP) is an
important starting material for the preparation of
cross-linking peroxides (dislkyl peroxides, such as e.g.
2,5-dimethYl-2~5-di-tert.-but~lperox~hexane~ or per-
ketsls, such as 3,3,6,6,9,9-hexameth~1-1,2,4,5-tetraoxa-
cyclononane)(cf GB-PS 935008), as well as of highl~
reactive bifunctional peresters.
In FR-PA 1291965 is admittedl~ also described the
preparation of 2,5-dimeth~1-2,5-di-tert.-but~lperox~-
hexane from 2,5-dimeth<yl-1,5-hexadiene by reaction with
tert.-butylhydroperoxide; however, the ~ield therebg
obtained of 26% is very unsatisfactor~ and, furthermore,
according to this process, onl~ dialk~lperoxides but no
perketal or perester derivatives of DHHP are obtainable.
As process for the preparation of 2,5-dimethyl-2,5-
dihydroperox~hexane (DHHP), from the prior art there is
known the react20n of 2,5-dimeth~lhexane with oxygen.
EP-A-0513711 describes a process for the prepsrstion
of aliph~tic h~droperoxides, e.g. of 2,5-dimethyl-2,5-
dih~droperoxyhexane (DHHP), bg re~cti~n of a corres-
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ponding tetrah~drofuran derivstive with h~drogen peroxide
US-A 4154768 describes a general process for the
preparation of tert.-alk~lh~droperoxides from as~mmet-
rical secondar~ olefins b~ reaction with hydro~en
peroxide in a reaction mixture containing a strong acid.
According to JP-A-3215468 snd JP-A-~i190856 ,. h~dro-
peroxides are obtained b~ reactioD of an oleftn or
alcohol with h~drogen peroxide in the presence of a
strong acid.
Usuall~, the preparation -of 2,5-dimeth~1-2,5-
dih~droperoxghexane (DHHP) takes plsce b~ reaction of
2,5-dimethglhexane-2,5-diol with h~drogen peroxide in
the pres.ence of an acidic catal~st, in ~eneral with the
use of sulphuric acid (cf.. Rust, J~ Am. Chem. Soc. 79
(1957) 4000, 4002; ~. Criegee, Erdol und Ko-hle, 15
I5 (1962) 523, 524,. 528; Criegee and Paulig~ ChemO Ber.
88 (1955), 712, 716; Criegee and Dietrmch~ Liebigs Ann~
Chem. 560 (1948) 141; L~. Dulog and A~ Sanner, Tetrahedron
~etters, 51 (1966) 6353-6358). ~ccording to the~e
processes, the dosing of the diol takes place 8~ solid
material, which i9 a disadvantageO A further disadvantage
of thi.s process is slso the eas~ formation of c~clisstion
products (e.g. 2,2,5,5-tetrameth~l.tetrah~drofuran) from
the diol under acid influence which i~ad~ to poor ~ields
of dih~droperoxide and a contaminsted product.
Therefore, there i5 still a ~reat need for a process
for the preparst~on of 2,5-dimeth~1-2,5-dih~droperox~-
hexane (DHHP) which can be carried out in simple and
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technicall~ sdvantageous wa~ and w-ith which the DHHP
is obtainable in high ~ield
ThiS task i~ sol~sd with the process of the
present invention~
The: subaect of the pre.seDt invention is a process
for the preparation of 2,5-dimeth~1-2,5-dih~droperox~-
hexane (DHHP~ according to claim 1 b~ reaction of
2,5-dimeth~1-1,5-hexsdiene with h~drogen peroxide in
an acidic medium.
A-t usual reaction temperatures,~ 8S .olefin 2,.5-
dimethgl-1~5-hexsdiene carcel~ reacts with an aqueous
mixture of hydrogen peroxide and sulphuric acid. However,
b~ addition of a Ymall amount df a suitable emulsifier
or of a solvent miscible with water,. a rapid reaction
to D~E~ takes place.
Therefore, the reaction is preferabl~ carried out
in an acidic aqueous medium with addition of sn emuls-
ifier or of a water-miscible solvent.
In the scop:e of the invention, as w~ter-miscibl~
solveDt thers can be used: trieth~l phosphate-,. tetra-
h~drofura.n, 1,4-dioxane, gl~cols or gl~col ethers, of
which trieth~l phosphste is especiallg preferred~
~ speciall~ suitable emulsifiers are non-ionic oxg-
eth~lates of aliphstic fatt~ alcohols or oxoalcohols
with 10 to 18 C-at~ms, such as C13/C15-oxoalcohol~
with 8 to 10 mol eth~lene oxide; C10-oxoalcohol with 6
to 7 mol eth~lene oxide; C13-oxoalcohol with 8 mol
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_5_
ethglene.oxide; C10/Cl2-fattg-alcohol propox~lated/
ethoxglated and sorbitan ester oxgeth~lates.
The reaction preferablg takes place alt a temperature
in the range of 0 to 60C and especiallg in the r~ange of
10 to 50C, whereb~, however, temperatures above or below
these ranges are also possible, especiallg depending upon
the reaction medium used and/or the acid used.
As acidic catal~st, an acid is preferabl~ used which
is selected from the group consisting of sulphuric acid,
phosphoric acid, alkglsulphonic acid, optionallg sub-
stituted arglsulphonic scids, polgphosphoric acid and
perchloric acid, wherebg sulphuric acid i~ especiallg
preferred.
In an especiall~ preferred embodimental form of the
process according to the invention, the 2,5-dimethgl-
1,5-hexadiene i5 added with stirring to an a~ueous
mixture of hgdrogen peroxide and sulphuric acid and
emulsifier.
The hgdrogen peroxide concentration is the reaction
medium preferablg amounts to 20 to 50 wt.% and especiallg
30 to 50 ~t..%; the hgdrogen peroxide ~s preferablg used
in a molar exces~ and especiall~ in a ratio of 1 mol of
2,5-dimet~ 1.,5-hexadiene to 3 to 8 mol and above all
of 5 mol of hgdrogen peroxide~
- 25 The gield o~ 2,5-dimeth~1-2,5-dih~droperox~hexane
(DHHP) obtainable bg the process according to the
invention is verg good and, as a rule,. amounts to at
21 88779
least 55~ (referred to 2,5-dimethgl-1,5-hexadiene).
Furthermore, b~ use of 2,5-dimeth~1-1,.5-hexadiene, a
starting material is also used which is a li~uid under
the process conditions, whereby a technicallg laborious
solid msterial dosing, as is nece~sar~ in the case of
the process for the prepsrstion of DHHP b~ reaction of
2,5-dimethglhexane-2,5-diol with h~drogen peroxide,
can be avoided~
The following E~amples are to explain the invention
in more detail without limiting it thereto.
Example 1
To a mixture of 194 g 70% h~drogen peroxide (4~0 mol),
150 g of 72~ sulphuric acid (1..1 mol) and 25 g of tri-
eth~l.phosphate are so added, with stirring and cooling,
1.5 113 g of 2,5-dimeth~1-1,.5-hexadiene (1~0 mol) in about
- 50 minutes that the temperature is maintained st 30C
~he DHHP alread~ begins to crgstallise after a few
minutes. After completed addition, it is further stirred
for 2 hours at 30C.
The resction mixture is dil.uted with 100 ml of water~
filtered and the DHEP washed with cold water~ One obtains
112~4 g of water-moi~t DHHP with a content of 80.4%
(corresponding to 50.7~ of the theoretical ~ield).
E~ample 2
To a mixture of 329 g of 70~ h~drogen peroxid~
(8.0 mol) and 218 g of 72~ sulphuric acid (1 6 mol) are
added 4 g of ~ween 21 (sorbitan monolaurate-4 EO). At
21 88~7~
25C, with stirring snd cooling, one so adds dropwi~
thereto 226 g 2,5-dimethgl-1,5-hexadiene ~2.0 mol)
that the temperature increases to 8 maximum of 35C.
After a few minutes, the DH~P begins to crgstallise~
After completed addition, one further stirs for 2 hours
at 30C, dilutes the reaction mixture with 250 ml of
water, filters off the DE~P and wahe~ it free of
h~drogen peroxide with cold water~ One obtains 310 g of
water-moist D~EP with a content of 73.4% (corres-
0 ponding to 63.8~ of the -theore~ical gield).
Examp~le 3
One proceeds as in Example 2 but adds to 301 g of
68~ h~drogen peroxide (6~0 mol) and 214 g of 65~
sulphuric acid (1~42 mol) 3 g of ~utensol ~0 8 (Cl~-
oxoalcohol with 8 mol ethgleDe oxide) and adds ~ropwisethereto 170 g of 2,5-dimethg~-1,5-hexadiene (1~5 mol).
One obtains 252 g of water-moist DHHP with a content
of 76~2% (co~responding to 71~8~ o~ the theoretical
gield)
E~ample 4
One proceeds as in Example 2 but adds to 315 g
of 68~ hgdrogen peroxide (6.~3 mol) and 210 g of 65%
sulphuric acid (1~39 mol) 2 g Marlox FK 86 E (C10/C12-
fattg alcohol propox~ated/ethoxglated) and adds drop-
wis~ thereto 113 g of 2,5-dimethgl-1,5-hexadiene (1 0
mol).
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One obtains 182 g of wster_moist DHHP with a
content of 75~1~; (corresponding to 74. 6~ of the
theQretica 1 ~ield) .
